Process of producing gasoline



H. B. sE'rzLER ESS GF PRODUCING GASGLINE May `4, 1927.

PROC

Filled June 9, 1916 mm Th1. me W5 :E

AT1 NEY.

Patented May 24, 1927.

UNITED STATES PATENT ori-10s.A

HORACE B. sE'rzLiiR, or coFFEYvIL A My invention relates to an improved pressure distillation, process ot producing gasoline, and is herein stituent of crude oil LE, KANSAS, ASSIGNOR T0 THE NATIONAL REFIN- ING COMPANY, 0F CLEVELAND, OHIO, A CORPORATION OF OHIO.

PROCESS 0F PRODUCING GASOLINE.

-Application led June 9, 1916. `Serial No. 102,651.

is not a natural conbut is a product obexeniplied as preferably practiced by the tained froi the natural constituents, by its pressure distillation of gas-oil, under consubjection Ioth to 5 ditions causing the extraction of carbon known methods, th

pressure and heat. fIn e carbon produced by therefrom. My object is to obtain, a ina-Xicracking the hydrocarbons, settles to the mum yield of gasoline with a minimum probottom of the still, and remains there; the

duction of gas and carbon, by a process that particles growing in mass, is substantially continuous, safe and comselves in a layer over th mercial in all respects. This application is Their presence is dangerous, a continuation in part of my prior appliiact that it is unsafe to opera cation Serial No. 57,358, filed October 22, pressure with al bottom. Therefore,

concentrate theme entire bottom. because of the te a still under f carbon upon its it is qui-te essential to It is highly desirable to start with la d isthe continuing performance ofv such proctillate having known characteristics containesses, that some device, or apparatus be proing natural constituents, which under ordivided, where known methods, distill4 is kept from depo over between temperatures of 450 F. and still. 675 F., having a gravity ot 32 to 34Baum. Prilimited thereto, marily, my object is to obtain from said practice thereof in the treatme distillates, products which under ordinary mercial product o conditions distill between temperatures oit' 80 F. and 350 F., and have a gravity of ranges between. 45 56 to 60 Baume; the properties of which specific gravity vhet are dissimilar to the properties of the natuyas obtained froml mi ral constituents. To this, end, I provide This is selected as typical and explanatory' means Jfor preventing the carbon, freed merely, since the temperatures and specific during the operation, from settling, concengravities o trating and depositing in a semi-crystalline my process an coke Jform, on the sheets of the still.

Until comparatively recent times, the art oif distilling petroleum, has consisted .prinmay best be esp cipally in separating its natural constituents, the accompanying drawings,

Fig. 1 -is a diagrammatic view nary conditions, and

' and grouping them into a series of products applicable for commercial use.v Gasoline, vation, partially broken away, showing apcommercially known as gas-oil,

While my invention is not I may readily explain the nt of the comcomprising a bon whose boiling point derivative hydrocar F., with a 0 and 675 ween 32 and 34: Baume, d-continent crude oil.

by the carbon, which splits 0E, siting lon the sheets of the t my invention, ion with keipsene, gas-oil,` lubricating oil and wax, paratus adapted for the practice of` my inwhen separated by distillation, and each vention.

Fig. 2 is a par product grouped separately, constitute natuu ral constituents found in the original mass a still equi of crude oil. 'Recently,'however, it has bean come important commercially, to break down or crack certain of the natural hydroline 3-3 of Fig. 2. carbons, as it has been termed, for the purpose of increasing the output ot gasoline, are indicated by pressure distillation.

Distilling under pressure has tor its object, the production of low boiling point dicated in Fig. 1: hydro-carbons; the properties of which are ber 1, equipped w dissimilar to the properties of the hydrosuch as the gas carbons from which they are obtained. Pres-, sure distillation therefore, must not be confounded with the normal atmospheric dischamber 4,' interme tillation, because the product sought in Vance of the chimney s pped for prac Fig. 3 is a view in cross-secti Throughou The assem tioned therein draftflue 3, comm tial longitudinal section of ticing my invention,

on thereof, on

drawings, similar parts by the same .character of` refbled treating apparatus is inJ comprisinga firing chamith suitable heating means, burner y2, forwardly posibeneath, the still. A down.-

unicates with the heating. diately positioned in adtack 5. The heat necessarily from combustion is applied to the bottom of the horizontal cylinder-still 7, which is set over and supported by front and rear end Walls, of the furnace and the combustion chamber. The still is provided with a gauge-glass 6, a manhole 8, a pressure gauge 9, and a thermometer 9'. A charging inlet pipe 10, enters the still at its top, near the front end; the charging being controlled by valve 11, past which oil is pumped through the preheating coils 4', by means of pump 12, receiving its supply from a tank not shown. An inclined vapor line 13, leaves the still near its rear end, and leads to aircondensing coils 14, and a condenser box. Beyond the condenser box is a valve 16, connected to a pipe leading to the receiving tank 17; the purpose of Which equipment is to carry of, condense and receive the products Which distill over., The inclined vapor line 13, is itself an air-cooler and is augmented by short angularly-extending members 13', Which assist in condensing.

The still 7, is equipped With a revolving shaft 18, mounted in water-cooled stuffing boxes 19, and itted With a pulley Wheel 20. Inside 4the still, there is attached to the shaft, a double helicoidal cleaner 21, of su-ch diameter and length-'as to engage the entire heated inner periphery of the still 7. At the front and rear ends of said shaft respectively, are Water pipes 22, 22', leading from a source not shown, and entering passages drilled in the ends of the shaft 18, a distance equal, at least to the length of the shaft inside the stuffing boxes. A discharge pipe is` attached to the still at its bottom, near the rear end, and to which is connected outlet pipe 24, leading througlil valve 25,1

to a cooling box 26, and thence through'the pipes 27, inside the box, and out through al valve 28, to a receiving tank 29.

A motor 30"' furnishes the power for driving the pulley Wheel 20connected to shaft 18. The double helicoidal vScrapers preferably are augmented by loops of chains 21', Which bear upon the bottom sheets of the horizontal still, and assist in preventing the adhesion of carbon.

With this description of convenient apparatus for practicing the same, I Will now explain, a process typical of my invention. The cylinder still 7, is charged with gas oil, We. may assume, having the characteristics previously explained, and to approximately one-half the full volume or capacity of the cylinder still; after which valves 11 and 16 are closed. Power is turned on the motor connected with pulley Wheel20, which rotates the helicoidal scraper or cleaner inside the still. The still is heated by the burner 2; the products of combustion being directed against the bottom of the still, so that the temperature of the contained oil,- rapidly rises, until it has reached about 700 F., at

which temperature the pressure begins to rise, and is indicated on the pressure gauge 9. By the time pressure has reached 40 t 60 pounds, the temperature will have risen to approximately 730 F., at which temperature and pressure,'carbon begins to split olf from the heated hydrocarbons; thereby producing new hydrocarbon compoundsdissimilar from the gas-oil, and having boiling points of 80 to 350 F., and a Baume gravity of 56 to 58. It Will be evident to those skilled in the art, that compounds having boiling points of 80 to/ 350 F., cannot, by reason of their inherent physical properties, remain in the still at the temperature referred to, hence they are permittedv to pass out through the vapor line 13, andare condensed in the coil 15, and thence conducted to the tank 17, by controlv of the valve 16.

A suitable safety-valve 15' may be provided in the pressureline to relieve any excessive or dangerous pressure generated. I have found thatgvvithout the use o f suitable cleaning, scraping, scouring or' ag 1 tating mean-s, carbon, at the instant 1t- 1s freed from its previous combination; being in a nascent state of amorphous character, and settling out of the mass of gas-oil, seems to be attracted,`or drawn to the heated bottom still sheet. Normally, these particles of carbon cohering together, and agglomerat ing over the bottom sheet, form a layer of carbon, assuming a semi-crystalline form, Which Would have the dangerous results heretofore explained. By using a helicoid cleaner, continuously revolving inside the still, and engaging the heated section of the inner periphery of the cylinder, or its equivalent, the carbon which has been freed from its combination, is retained in an amorphous condition, and suspended throughout the mass of oil. Any carbon, which by chance is attracted or becomes momentarily attached to the bottom, cannot remain there, because the blades of the helicoid and chains engaging the bottom, sweep the particles of carbon away in their course of travel.

In addition, the helicoid performs several advantageous functions. lt is slowly revolved, and in a direction carrying the gasoil from the front to the rear of the still. Being in constant contact with the heated bottom sheets, said helicoid becomes hi hly heated and serves to `dis-tribute the ealt throughout the interior of the still ;-and thus the heat is communicated directly to the vapors in said space above the gas oil, as Well as to the fluid itself; thereby greatly facilitating the practice Vof my improved process. It has catalytic action, as Well.

Hydrocarbons ultimately may be degraded down to permanent gases and solid carbon by `the influence of heat, and by the proper regulation of the same, intermediate products between carbon and permanent gases, can be produced, but as far as I am aware, no device br apparatus previously has been employed to extract and maintain the car-` bon. in an amorphous condition, while the process is progressing. It is apparent then, that the degradation or decomposition of hydrocarbons, necessarily means the extraction of carbon, which is the clogging element in the successful performance of any pressure operation. This I have overcome .by the means referred to, and in addition, by suitably controlling the re-action, I produce a minimum, both ofcarbon and fixed gas.

In practicing my process, the gas-oil or other hydrocarbon supplied to the still, is subjected to high temperatures andI moderate pressures, and the chemical aifinity of its elements being partially overcome, certain of the combined carbon atoms are split off in amorphous condition, and are maintained, in that condition by `continued agitation. When the chemical affinity between the carbon and hydrogen has been broken, the existing chain of hydrocarbons is opened, and a new seriesis produced, which cannot remain in the highly heated still, because of their low boiling point. Consequently, they are permitted from time to time, to pass out through the vapor line.

After the described operation has progressed, until approximately 10% of thev .volume of gas-oil charged into the still has been converted into other products boiling between 80 and 350" F., and the 'Baum 4 gravity of said products is found to range from 56 to 58, as indicated by the hydrometer on samples taken from the end of the pipe entering tank 17, the pump 12 is started. Grasoil i's continuously'pumped in through the heating coils 4', and the line 10, regulated by and throughl valve 11, entering the still at the frontend, at the same time the new products referred to, are lconducted of through the vvapor line 13. Any convenient device 'may be used, such as meters 30, 31, to establish the ratio of a constant quantity of gas-oil, entering the^still at the front end,

anda corresponding quantity of products passing off, and collecting in the receiving tank 17. i

Having established the quantity entering and leaving the still,^ftle'operation is continued. The valve 25,-connected by a pipe to the trap on the bottom, nearthe rear end of the still, istheii operated for the-purpose of drawing off the contents, either continuously or periodically; measuring it through a` meter 32, after. the liquid hasv passed lthrough thecoils 27, submerged inthe cooling box 26. i

In the instance assumed, the Baume gravity of the oil iii the still will have reached found, that with the gas-oil referred to,

approximately 24, at which gravity I begin to draw o the contents at the rear end of the still, but I wish it understood that the gravity test referred to is not invariable. The figures were used merely to indicate the preferred Inode of operation,

I can go lower, with no apparent deposit on its bottom, if thescoiiring action be continued, and the operation proceeds regularly under these conditions.

From the foregoing it Will be seen that the described process is capable of indefinite continuation, depending somewhat upon the character of the hydrocarbons treated. The liquid condensed and collected in tanks 17, may be distilled in the ordinary manner, primarily for their gasoline content, While the heavier distillates therefrom, may be mixed with the contents of tank 29, and reintroduced into the still 7, for further treatment, if desired. Connected with the intermediate tank 33 is a pressure gauge 30, which may be used for controlling the continued practice of the described process, but as these stcpsform no part of they need not be further referred to herein.

It is apparent that the mechanism provided, serves continuously to agitate the contents of the still, and such agitation, moreover, is coupled with the repeated scouring and scraping of the bottom of said still; all

of which contribute to the retention of the carbon infits amorphous form, and prevent its adherence to the bottom plates of said still. In addition, thereto', blades 21, may be formed of copper or copper alloy, instead of steel, and may be substituted or augmented by chains or brushes of any material, adapted to afford catalytic action, and therefore 'promote thecheinical re-actions within the still. .'lhese, further features, however, as well as the precise apparatus herein described, forni no essential part of my present invention.

Insteahxpmy invention is concerned' with the method of extracting carbon froi'ii hydrocarbons by their decomposition iiiider conditions pernnttliigthe control of the reactions, wherebythe existing chains of the hydrocarbons aie opened and a new series is produced. The process essentially conmy invention,

and I Vhave Iii() the helicoidal sists iii distilling a suitable hydrocarbon, Y

preferably gas-oil, under a relatively -low pressure, i. e., within a range of from-10 to 100 pounds, and at temperatures Within a range of from 700 to-750 F. -Meantiine,

the gas-oil is maintained at a substantially constant level within the still, by pumping in fresh andv preferably preheated fluid, so that there is approximately a pressure space within the still of half its volume. Throughout the entire process, the motion of. the ,I

helicoid is continued for the purpose of scraping the bottom, carrying the heat to the carbon extracting or. process of free-4 throughout the interior of. the still, and

gradually conveying the heavier hydrocarbons toward the discharging end of the still. This process, moreover, may well-be augmented by the reflux of the lower boiling point hydrocarbons, from the vapor line into the still, so that they Amay be subjected ing the carbon above described, and obtain a maximum yield of hydrocarbons, from which commercial gasoline may be distilled.

The'process lherein described differs from any other with which I am acquainted, by reason of the fact that under favorable conditions, I have been able to produce a yield of from 40 to 50 per cent of gasoline, with the extraction merely of from 3 to 8 ounces of carbon, and the production of fixed gases approximating 20 to 30 cubic feet only per The preferred pressureA barrel of gas-oil. approximates 60 pounds per square inch, and I have foundthat by maintaining the pressure relatively low, throughout the vapor line, that the yieldof fixed gases is materially reduced, thereby augmenting the. production of gasoline. The importance of the helicoid, as a member serving to maintain the heated bottom sheets free from car-v bon, conveying the treated hydrocarbon and extracted carbon toward the point of discharge, anddistributing the heat through the fluid and vapor space within the still,` V.can scarcely be over-estimated, inasmuch as l the successful vpractice of the process is decarbon from gas-oilv to produce gasoline,

which consists in subjecting the gas-oil to pressure-distillation in akvolumemaintained substantially constant under conditions in- '.si'gnaturp volving a pressure of from to 100 pounds, temperatures of from 700 to 750 F., within a highly heated pressure space approximately equal to the volume of gas-oil under treatment; meanwhile subjecting the gasoil to suitable means for concurrently scouring the bottom of the still, and advancing the treated hydrocarbons to the point of withdrawal, substantially as set forth.

2. A process involving the separation of carbon from gas-oil to produce gasoline, which consists in subjecting the gas-oil to pressure distillation in a volume maintained substantially constant under conditions involving a pressureof from 50 to 100 pounds, andtemperatures of from 700 to 750 F.,

within a highly heated, pressure space approximately equal to` the volume of gas-oil under treatment; meanwhile maintaining a.

supply of preheated gas-oil, and subjectingthe treated gas-oil to a highly heated moving member serving to free the bottom of thestill from carbon deposit, substantially as set forth.

3. A process for treating petroleum or its derivatives, which consists in conducting pressure distillation thereof under conditions insuring a relatively large pressure space in the container, mean time maintaining the freed carbon in finely divided state and suspension, while subjecting the treated derivatives and pressure space to the actionl of a highly heated moving member introducing a preheated supply of hydrocarbons and withdrawing the newly formed hydrocarbons from the container, substantially as set forth. t

4. A process involving the separation of carbon from gas-oil to produce gasoline, which consists in heating 1t at temperatures approximating 700 F. under pressures adapted for cracking in a suitable still; meantime maintaining the freed carbon in a state of suspension, withdrawing the newly formed hydrocarbons effecting thel reflux of Aheavier distillate factions and'supplying proportionate quantities of gas-oil in preheated condition, substantially as set forth.

lin testimony whereof I do now affix -my Y HORACE B. sE'rzI-,ER 

